Radical reactivity of antiaromatic Ni(II) norcorroles with azo radical initiators

Norcorrole is a stable 16π antiaromatic porphyrinoid that exhibits characteristic reactivities and physical properties. Here, we disclose the reaction of Ni(II) norcorroles with alkyl radicals derived from azo radical initiators. The radical selectively attacked the distal α-position to the meso position to construct a non-aromatic bowl-shaped structure. The photophysical and electrochemical properties of the obtained radical adducts were compared with those of the parent Ni(II) norcorrole. The radical reactivity of Ni(II) norcorroles was investigated by density functional theory (DFT) calculations.